RU2572816C2 - Multilayer nanocomposite for two-coating capacitors and method of its manufacture - Google Patents

Abstract

FIELD: electricity.

SUBSTANCE: nanocomposite contains a substrate from conductive material with nanostructured coating located on its face surface and which is a lower coating of the capacitor which is made as a layer of carbon fabric, base threads and filler of which are formed by the activated carbon fibres twisted in the longitudinal direction. Base threads and filler of the named fabric mechanically and electrically by means of conductive glue are connected to the conductive substrate in places of adjunction to the conductive substrate of their sections, upwarped towards the conductive substrate, meanwhile in each glue connection of base threads and filler with the conductive substrate the maximum depth of penetration of conductive glue into structure of the named threads amounts from 0.3 to 0.5 of the transversal sizes of threads. On the surface of fibres of the base threads and filler are located in series and conformally to these surfaces at least one layer from dielectric material functioning as a top coating, and conductive material layer. Also the method of manufacture of multilayered nanocomposite comprising its heating in a neutral atmosphere up to the temperature, corresponding to maximum temperature of atom and layered sedimentation with endurance at this temperature until achievement of constant weight is offered.

EFFECT: improvement of homogeneity and specific surface of the nanostructured coating.

3 cl, 1 dwg

Description

The invention relates to microelectronics, and more particularly, to metal-dielectric-metal structures for capacitors with a large specific energy and electric intensity, as well as with nanometer-thick layers.

A multilayer nanocomposite for double-walled capacitors is known, which contains a dielectric substrate, for example, a glass one, with a nanostructured coating located on its front surface, which is made of anodic aluminum oxide, and on the surface of the said coating and conformally arranged in series: the first layer of titanium nitride (thickness 5, 6 nm), an alumina layer (6.5 nm thick) and a second titanium nitride layer (12.6 nm thick) formed by atomic layer deposition (see Parag Banerjee and al. Nanotubular metal-insulator-metal capacitor arrays for energy storage. Nature Nanotechnology, v. 4, pp. 292 ÷ 296, 2009).

It also describes a method of manufacturing a multilayer nanocomposite for double-walled capacitors, which includes forming on the front surface of a dielectric substrate, for example, a glass, nanostructured coating in the form of a layer of anodic aluminum oxide by electrochemical anodizing in an aqueous electrolyte a layer of ultrapure aluminum, previously deposited on the front surface of the substrate, and subsequent application by atomic layer deposition on the porous surface of the coating first lower cover ki (the first layer of titanium nitride with a thickness of 5.6 nm), then the dielectric layer (layer of alumina with a thickness of 6.5 nm), and then the upper lining (second layer of titanium nitride with a thickness of 12.6 nm).

Since the layers of anodic alumina have a nanosized cellular-porous structure, which is characterized by a high degree of orderliness, as well as the location of the pore axes at the same angle to the surface of the layer, therefore, the technical solution described above ensures high reproducibility of the electrophysical parameters of the capacitors made using it.

However, the need to form two layers of an electrically conductive material (in other words, the impossibility of using a substrate as one of the capacitor plates) not only leads to a complication of the design of a multilayer nanocomposite and to an increase in the duration of its manufacture, but also imposes strict upper restrictions on the thickness of the dielectric layer, since the maximum the transverse pore size obtained by the method of anodizing ultrapure (99.99%) aluminum known from the prior art is about 50 nm (see Report hells of the Belarusian State University of Informatics and Radioelectronics, 2 (14), pp. 127 ÷ 183, 2006). In addition, the implementation of the lower lining of the capacitor in the form of a metal layer of nanometer thickness creates serious difficulties in forming an electrical outlet to it, and therefore leads to an increase in the cost of the final product - the capacitor. The disadvantages of the analogue described above should also include the need to use a coating for the front surface of the substrate, which is not industrially produced, resulting in an increase in the cost of a multilayer nanocomposite for double-walled capacitors.

As a prototype, we took a multilayer nanocomposite for double-walled capacitors, containing a substrate of an electrically conductive material (preferably semiconductor, for example silicon) with a nanostructured coating located on its front polished surface, which is made in the form of an array of carbon fibers (filaments) with nanometer transverse dimensions that are disordered on the front surface of the substrate and have mainly upward curved axes, while on the surface fibers and on areas of the front surface of the substrate that are not occupied by said fibers, a nanometer-thick layer of dielectric material is conformally conformable to these surfaces, and a layer of nanometer-thickness of electrically conductive material serving as a top sheath is located on the surface of the dielectric material and conformally on its surface, preferably from titanium nitride. The said layers of dielectric and electrically conductive materials are formed by atomic layer deposition (see C.Y.H. Chow, R.C. Dubrov, US-B1 patents No. 7295419, 2006 and No. 7466533, 2007).

A method of manufacturing the multilayer nanocomposite for double-walled capacitors described above includes forming on the front polished surface of a substrate of an electrically conductive material (preferably a semiconductor, for example silicon) nanostructured coating in the form of an array of carbon fibers (filaments) with nanometer transverse dimensions. To do this, first, on the front surface of the substrate, many nanoscale surface regions of initial growth (centers initiating the formation of nuclei) are formed in the form of one-dimensional nanoelements from an electrically conductive material by spraying particles of cobalt or nickel that catalyze the nucleation of carbon, and then one-dimensional nanoelements in the form of carbon fibers are grown on the substrate . Then, on the surface of the mentioned fibers and on the surface portions of the substrate not occupied by these fibers, a layer of dielectric material is applied by atomic layer deposition to these surfaces conformally and then a layer of electrically conductive material is applied onto the entire surface of the layer of dielectric material and conformally to its surface (see A Farcy et al. WO 2008/04706, A1, pp. 8 ÷ 12, 15 ÷ 18, fig. 3A ÷ 3E, 4, 6A, 7A ÷ 7G).

The main disadvantage of the prototype is that its manufacture is fraught with considerable difficulties, since the formation of a nanostructured coating in the form of an array of carbon fibers (filaments) with nanometer transverse dimensions on the front surface of the substrate is carried out as a result of complex technological operations that also require the use of complex and expensive equipment . A consequence of the above is the significant cost of the final product - the capacitor.

In addition, due to the low mechanical strength of carbon fibers, an increase in the surface development of a nanostructured coating by increasing the length of carbon fibers (up to 0.1 ÷ 0.5 mm) leads not only to additional difficulties in the manufacture of a multilayer nanocomposite for double-walled capacitors, but, most importantly, to a significant spread in the length of carbon fibers in the nanostructured coating, and therefore to a significant spread in such a parameter as the capacitance of capacitors made according to rototipu.

The present invention is aimed at solving the technical problem of creating a multilayer nanocomposite for double-walled capacitors, the design of which, due to the implementation of a nanostructured coating from industrially produced activated carbon fabric, provides a significant simplification and cheapening of the method of its manufacture while providing a uniformly distributed substrate surface and a high (at least 10 ³ m ² / g) specific surface area of the nanostructured coating. The technical result achieved by performing a nanostructured coating from industrially produced activated carbon fabric, which consists in simplifying the method of manufacturing a multilayer nanocomposite for double-walled capacitors, is due to the fact that instead of operations associated with the formation on the front surface of the substrate of a nanostructured coating in the form of an array of carbon fibers (filaments ) with nanometer transverse dimensions and requiring the use of a special layer expensive and expensive equipment, only one operation is used, namely, gluing the finished activated carbon fabric to the front surface of the electrically conductive substrate, which does not require the use of complex and expensive equipment or significant time costs.

и $$M_y^{-1}$$

.From the point of view of the device, the problem is solved in that in a multilayer nanocomposite for double-walled capacitors, containing a substrate of an electrically conductive material with a nanostructured coating located on its front surface and being the bottom of the capacitor, as well as at least one layer of dielectric material and performing function of the upper lining of the capacitor a layer of electrically conductive material formed by atomic layer deposition, according to the invention, a nanostructure ingly coating is a layer of carbon fabric, the warp and weft is formed by activated carbon fibers, twisted in the longitudinal direction relative to their corresponding axis of the yarn with the number of twists - M _o per unit length of the warp yarns and the number of twists - M _y per unit length weft threads, warp threads and weft of said fabric are mechanically and electrically connected by means of an electrically conductive adhesive to the electrically conductive substrate at the points of contact with the electrically conductive substrate, areas toward the electrically conductive substrate, while in each adhesive connection of the warp and weft threads to the electrically conductive substrate, the maximum penetration depth of the electrically conductive adhesive into the structure of said filaments is from 0.3 to 0.5 of the transverse size of the filaments, and on the surface of the fibers of the warp and weft filaments at least one layer of a dielectric material and a layer of an electrically conductive material that is arranged as a top sheath are arranged sequentially and conformally to these surfaces, the dimensions of the electric the conductive substrate corresponding to each capacitor, in the direction of the warp and weft, is not less, respectively $$M_o^{-\mathrm{one}}$$

and $$M_y^{-\mathrm{one}}$$

.

In addition, in a preferred embodiment of the invention, the substrate is made of a semiconductor material, for example silicon, with a polished front surface.

From the point of view of the method, the problem is solved in that in the method of manufacturing a multilayer nanocomposite for double-walled capacitors, including the formation of a nanostructured coating on the front surface of the electrically conductive substrate, as well as atomic-layer deposition onto the developed surface of the nanostructured coating and conformally sequentially at least at least , one layer of dielectric material and a layer of electrically conductive material according to the invention as nanostructures of the urinated coating, activated carbon fabric is used, which is glued to the front surface of the electrically conductive substrate with an electrically conductive adhesive to provide warp threads and weft of activated carbon fabric to be connected to the electrically conductive substrate by connecting them to areas that are convexly curved towards the electrically conductive substrate, as well as providing warp and weft threads with an electrically conductive substrate in each adhesive joint the maximum penetration depth of the electrically conductive adhesive into the structure of the said filaments is from 0.3 to 0.5 of their transverse size, and before applying the method of atomic layer deposition on the developed surface of the nanostructured coating and conformally to it at least one layer of a dielectric material and a layer of an electrically conductive material, the substrate, together with a nanostructured coating located on its front surface, is heated in an inert atmosphere to a temperature corresponding to the maximum rate Aturi during atomic layer deposition operations, followed by exposure at this temperature until reaching constant weight.

The advantage of the patented multilayer nanocomposite for double-walled capacitors (compared to the prototype) is that, instead of using a nanostructured coating, formed by growing directly on the front surface of the electrically conductive substrate an array of randomly spaced carbon fibers with nanometer transverse dimensions and mainly curved axes pointing upwards, patentable nanostructured coating characterized by the above set of essential features, provides not only the simplification and cheapening of the method of its manufacture, but also a significant reduction in the cost of the final product - capacitors while significantly reducing the dispersion of their electrophysical parameters. The remaining technical results achieved by using the patented invention will become clear from the further discussion, while the premise of the patented invention is the results of studies by scanning electron microscopy and standard porosimetry of the side surface of activated carbon fibers, of which warp and weft of industrially produced activated carbon fibers are made tissues. Thus, studies of activated carbon fibers by scanning electron microscopy showed that these fibers have a regular cylindrical shape and a diameter of about 10 microns. At the same time, activated carbon fibers have a strongly developed lateral surface formed by a multitude of not only mesopores (with a diameter of 30 to 50 nm), but also macropores (with a diameter of 50 to 300 nm) that are radially arranged relative to the fiber axis. Studies of activated carbon tissue samples by standard porosimetry also showed that the developed lateral surface of activated carbon fibers is formed by mesa and macropores, and it was found that when applying the material directly onto the surface of said fibers by atomic layer deposition, it is advisable to use a precursor with hydrophobic properties, for example trimethylaluminum. Thus, the geometrical parameters of the developed lateral surface of activated carbon fibers provide the possibility of forming by atomic layer deposition on their lateral surface and conformally at least one layer of dielectric material and a layer corresponding to the upper lining of the capacitor of the electrically conductive material. In other words, on the basis of studies of the lateral surface of activated carbon fibers, it was established (obviously not the following from the prior art) that it is possible to use industrially produced activated carbon fabrics for the manufacture of a multilayer nanocomposite for double-walled capacitors, while for the practical implementation of this possibility, a patented implementation of electromechanical compounds of activated carbon fibers with an electrically conductive substrate.

The invention is further illustrated by a specific example, which, however, is not the only possible one, but clearly demonstrates the possibility of achieving the aforementioned technical result with a patentable combination of essential features.

The drawing schematically on an enlarged scale and in section shows the implementation of adhesive bonding of warp and weft of activated carbon fabric with an electrically conductive substrate, while in order to simplify the drawing, activated carbon fibers forming warp and weft are not shown.

The following notation is used in the drawing: 1 - electrically conductive substrate; 2 - warp threads of activated carbon fabric; 3 - weft threads of the same fabric; 4 - conductive adhesive.

A multilayer nanocomposite for double-walled capacitors contains a substrate of electrically conductive material (preferably semiconductor, for example silicon) with a nanostructured coating located on its front surface (preferably polished) and in the form of a layer of industrially produced activated carbon fabric, preferably with a plain weave type in which the warp and weft overlap each two successive overlappings with m the minimum rapport, as well as having a thickness of 0.3 to 0.4 mm and a specific surface area of at least 10 ³ m ² / g (for example, activated carbon fabric of Busofit T-055 6-97 or Busofit T-055 2 brands -21 * 29 ”, manufacturer of the RUE“ SPA “Khimvolokno”, Svetlogorsk, Republic of Belarus), while the warp and weft of this fabric are formed by activated carbon fibers with a diameter of about 10 μm, which are twisted in the longitudinal direction relative to the axis of the corresponding thread with the number twist - М _о per unit length of threads of 2 warp and with the number of twists - М _y per unit of length of threads 3 weft. Moreover, in most cases, M _o = M _y = 200 ÷ 250 m ^-1 . As noted above, activated carbon fibers have a developed lateral surface formed by meso- and macropores radially located relative to the fiber axis, as well as a low electrical resistivity of the order of 5 · 10 ^-2 Ohm · cm. Activated carbon tissues are characterized by a high and uniformly distributed specific surface area (up to 2.5 · 10 ³ m ² / g) and are used in medicine as antibacterial dressings in the treatment of burns and wounds (see Sorbents and their clinical use. Ed. K. Giordano, Kiev: Higher School, 1989, 400 pp.), In technical electrochemistry for the manufacture of energy storage devices and ultra-high capacitors (see Hang Shi. Electochim. Acta, v.41, No. 10, p.1633-1689. 1996), in the hydrometallurgy of precious, rare and non-ferrous metals, for the removal (extraction) of allov from wastewater (see. Varentsov VK Proc .: Intensification electrochemical processes. Ed. Tomilova AP. M .: Nauka, 1988, s.94-118). The warp threads 2 and the weft threads 3 (see drawing) of the activated carbon fabric are mechanically and electrically by means of an electrically conductive adhesive 4 (for example, EPO-TEK ^® H20E silver-based electrically conductive adhesive) connected to the electrically conductive substrate 1 at the abutment (contact, touch) ) of each of them to the electrically conductive substrate 1. In other words, the warp yarns 2 and the weft yarns 3 are connected by means of an electrically conductive adhesive to the electrically conductive substrate at the points of contact with the electrically conductive substrate, they are convex from the sections bent towards the electrically conductive substrate, while in each adhesive connection of the warp threads 2 and the yarn 3 weft with the electrically conductive substrate 1, the maximum depth Δ of the penetration of the electrically conductive adhesive 4 into the structure of the said filaments is from 0.3 to 0.5 of the transverse dimension - D threads , in other words, Δ = (0.3 ÷ 0.5) · D. At least one layer of dielectric material and a layer of electrically conductive material, preferably titanium nitride, formed by atomic layer deposition are arranged sequentially and conformally to these surfaces on the surface of the fibers of the warp threads 2 and the weft 3. In a preferred embodiment of the invention, the dielectric part of the patented nanocomposite is made of a two-layer of dielectric materials with different dielectric constant and electric strength (similar to that described in the patent: Vargan V.A. et al. RU 2432634, C1, 2011), which, as you know, provides both an increase in capacitance and breakdown voltage of capacitors, and, consequently, an increase in energy intensity. In this case, the first layer of the dielectric part of the patented nanocomposite is made of amorphous alumina and is arranged conformally to the surface of the fibers of warp 2 and weft 3, while the second layer of rutile modification titanium dioxide is located conformally to the surface of the first layer of dielectric material, while the layer thickness lies in range from 5 to 20 nm.

и $$M_y^{-1}$$

.As for the dimensions of the electrically conductive substrate corresponding to each capacitor, its dimensions in the direction of warp threads 2 and weft threads 3 are not less, respectively $$M_o^{-\mathrm{one}}$$

and $$M_y^{-\mathrm{one}}$$

.

или $$M_y^{-1}$$

) электрическое соединение (электрический контакт) большей части активированных углеродных волокон каждой упомянутой нити с электропроводящей подложкой 1. Действительно, поскольку нити 2 основы и нити 3 утка активированной углеродной ткани образованы активированными углеродными волокнами, скрученными в продольном направлении относительно оси соответствующей им нити, то распределение активированных углеродных волокон по поперечному сечению нити в пределах одного клеевого соединения будет отличаться от распределения активированных углеродных волокон по поперечному сечению той же нити на участках, соответствующих другим клеевым соединениям ее с электропроводящей подложкой 1 и расположенных на длине каждой упомянутой нити, соответствующей одной скрутке соответствующих ей активированных углеродных волокон на 360° относительно ее оси (иными словами, на длине, равной $$M_o^{-1}$$

или $$M_y^{-1}$$

). В результате, в каждом клеевом соединении каждой нити с электропроводящей подложкой 1, расположенном в пределах длины нити, соответствующей одной скрутке соответствующих ей активированных углеродных волокон на 360° относительно ее оси, осуществляется электрическое соединение с электропроводящей подложкой 1 различных групп активированных углеродных волокон соответствующей нити без существенного уменьшения площади развитой поверхности активированной углеродной ткани за счет того, что пропитанный электропроводящим клеем объем каждой нити минимален. Так, при Δ=0,25D и на длине нитей 2 основы, равной $$M_o^{-1}$$

, а также на длине нитей 3 утка, равной $$M_y^{-1}$$

, обеспечивается электрическое соединение от 72 до 74% активированных углеродных волокон нитей основы и утка активированной углеродной ткани с электропроводящей подложкой 1 при уменьшении площади развитой поверхности активированной углеродной ткани 6÷7%. При Δ=0,3D и на длине нитей 2 основы, равной $$M_o^{-1}$$

, а также на длине нитей 3 утка, равной $$M_y^{-1}$$

, обеспечивается электрическое соединение от 85 до 88% активированных углеродных волокон нитей основы и утка активированной углеродной ткани с электропроводящей подложкой 1 при уменьшении площади развитой поверхности активированной углеродной ткани 9÷11%. При Δ=0,5D и на длине нитей 2 основы, равной $$M_o^{-1}$$

, а также на длине нитей 3 утка, равной $$M_y^{-1}$$

, обеспечивается электрическое соединение от 98 до 100% активированных углеродных волокон нитей основы и утка активированной углеродной ткани с электропроводящей подложкой 1 при уменьшении площади развитой поверхности активированной углеродной ткани 13÷17%. Здесь необходимо отметить, что выполнение клеевых соединений с Δ>0,5D нецелесообразно, поскольку это приводит к дальнейшему уменьшению площади развитой поверхности активированной углеродной ткани.Patented performance of adhesive bonding of warp threads 2 and threads 3 weft of activated carbon fabric with an electrically conductive substrate 1 in the form of sections located at the same pitch along the length of each said yarn and corresponding to the points of contact of each said yarn with the electrically conductive substrate 1, within each of which the maximum penetration depth electrically conductive adhesive 4 in the structure of the said filaments is from 0.3 to 0.5 of their transverse size, on the one hand, provides a reliable mechanical connection By adding regular carbon fiber to said activated carbon fabric yarn 1 with regular (with the same pitch) arrangement of adhesive joints along the entire length of each of these yarns, on the other hand, it ensures, along the length of each yarn, corresponding to one twist of 360 activated carbon fibers corresponding to it ° relative to its axis (in other words, at a length equal to $$M_o^{-\mathrm{one}}$$

or $$M_y^{-\mathrm{one}}$$

) the electrical connection (electrical contact) of most of the activated carbon fibers of each of said yarns with the electrically conductive substrate 1. Indeed, since the warp yarns 2 and the weft yarn 3 of the activated carbon fabric are formed by activated carbon fibers twisted in a longitudinal direction relative to the axis of the corresponding yarn, the distribution activated carbon fibers in the cross section of the thread within one adhesive connection will differ from the distribution of activated glerodnyh fibers across the cross section of the same filament on the portions corresponding to the other adhesive compounds it with the electroconductive substrate 1 and located on the length of each of said thread corresponding to one twisting corresponding to it activated carbon fibers of 360 ° about its axis (in other words, a length equal to $$M_o^{-\mathrm{one}}$$

or $$M_y^{-\mathrm{one}}$$

) As a result, in each adhesive connection of each filament with the electrically conductive substrate 1, located within the length of the filament corresponding to one twist of its activated carbon fibers 360 ° relative to its axis, an electrical connection is made to the electrically conductive substrate 1 of different groups of activated carbon fibers of the corresponding filament without a significant reduction in the area of the developed surface of activated carbon tissue due to the fact that the volume of each impregnated with electrically conductive adhesive threads are minimal. So, at Δ = 0.25D and on the length of the threads 2 of the warp equal to $$M_o^{-\mathrm{one}}$$

, and also on the length of the threads 3 weft equal to $$M_y^{-\mathrm{one}}$$

provides an electrical connection from 72 to 74% of the activated carbon fibers of the warp and weft of the activated carbon fabric with an electrically conductive substrate 1 while reducing the developed surface area of the activated carbon fabric by 6-7%. When Δ = 0,3D and on the length of the threads 2 warp equal to $$M_o^{-\mathrm{one}}$$

, and also on the length of the threads 3 weft equal to $$M_y^{-\mathrm{one}}$$

provides an electrical connection from 85 to 88% of the activated carbon fibers of the warp and weft of the activated carbon fabric with the electrically conductive substrate 1 while reducing the developed surface area of the activated carbon fabric by 9 ÷ 11%. When Δ = 0,5D and on the length of the threads 2 warp equal to $$M_o^{-\mathrm{one}}$$

, and also on the length of the threads 3 weft equal to $$M_y^{-\mathrm{one}}$$

provides an electrical connection from 98 to 100% of the activated carbon fibers of the warp and weft of the activated carbon fabric with the electrically conductive substrate 1 while reducing the developed surface area of the activated carbon fabric 13 ÷ 17%. It should be noted that the implementation of adhesive joints with Δ> 0.5D is impractical, since this leads to a further decrease in the developed surface area of activated carbon fabric.

и $$M_y^{-1}$$

, количество активированных углеродных волокон в каждой упомянутой нити, механически и электрически соединенных с электропроводящей подложкой 1, увеличивается незначительно (не более чем на 4%) за счет нерегулярного (неупорядоченного) расположения активированных углеродных волокон по поперечному сечению упомянутых нитей в их продольном направлении. Таким образом, при выполнении электропроводящей подложки, соответствующей каждому конденсатору, с размерами в направлении нитей 2 основы и нитей 3 утка меньше соответственно $$M_o^{-1}$$

и $$M_y^{-1}$$

будет иметь место сильная зависимость количества активированных углеродных волокон в каждой упомянутой нити, механически и электрически соединенных с электропроводящей подложкой, от размеров электропроводящей подложки 1 в упомянутых направлениях, а следовательно, имеет место сильная зависимость электрофизических параметров конечного продута от размеров подложки, соответствующей каждому конденсатору. На основании вышесказанного, а также учитывая, что патентуемое наноструктурированное покрытие характеризуется не только более высокой (по сравнению с прототипом) удельной поверхностью, но и более высокой однородностью распределения ее по поверхности подложки, можно сделать вывод, что патентуемое изобретение обеспечивает достижение также технического результата, заключающегося в возможности создания двухобкладочных конденсаторов с контролируемыми электрофизическими параметрами (за счет обеспечения контролируемого количества межсоединений активированных углеродных волокон в каждой упомянутой нити с электропроводящей подложкой) на базе патентуемого многослойного нанокомпозита для двухобкладочных конденсаторов, имеющего соответственно для каждого конденсатора размеры подложки вдоль нитей 2 основы не меньше $$M_o^{-1}$$

, а вдоль нитей 3 утка не меньше $$M_y^{-1}$$

.In addition, it was found that when the length of the threads 2 warp and threads 3 weft, respectively exceeding $$M_o^{-\mathrm{one}}$$

and $$M_y^{-\mathrm{one}}$$

, the amount of activated carbon fibers in each of the aforementioned threads mechanically and electrically connected to the electrically conductive substrate 1 increases insignificantly (by no more than 4%) due to the irregular (disordered) arrangement of the activated carbon fibers in the cross section of the said threads in their longitudinal direction. Thus, when performing an electrically conductive substrate corresponding to each capacitor, with dimensions in the direction of the warp threads 2 and the weft threads 3, respectively, less $$M_o^{-\mathrm{one}}$$

and $$M_y^{-\mathrm{one}}$$

there will be a strong dependence of the amount of activated carbon fibers in each of said yarns mechanically and electrically connected to the electrically conductive substrate on the dimensions of the electrically conductive substrate 1 in the mentioned directions, and therefore, there will be a strong dependence of the electrophysical parameters of the final product on the dimensions of the substrate corresponding to each capacitor. Based on the foregoing, and also considering that the patented nanostructured coating is characterized not only by a higher specific surface (as compared with the prototype), but also by a higher uniformity of its distribution over the surface of the substrate, we can conclude that the patented invention also provides a technical result, consisting in the possibility of creating double-walled capacitors with controlled electrophysical parameters (by providing a controlled amount of inter compounds of activated carbon fibers in each of said filaments with an electrically conductive substrate) based on the patented multilayer nanocomposite for double-walled capacitors having respectively for each capacitor the dimensions of the substrate along the warp threads 2 are not less than $$M_o^{-\mathrm{one}}$$

and along the threads 3 weft no less $$M_y^{-\mathrm{one}}$$

.

A method of manufacturing a multilayer nanocomposite for double-walled capacitors is as follows. First, similar to the prototype, a nanostructured coating is formed on the front surface of the electrically conductive substrate, in which the patented invention uses an industrially produced activated carbon fabric, preferably with a plain weave type, in which the warp and weft overlap each two successive overlaps with minimal repetition while the warp and weft of the activated carbon fabric are formed by activated carbon fibers Twisted in the longitudinal direction relative to their corresponding axis of the yarn with the number of twists - M _o per unit length of the warp yarns and the number of twists - M _y per unit yarn length of the weft, for example an activated carbon cloth, for example activated carbon cloth mark "Busofit T-055 6 -97 ”(producer of RUE“ SPA “Khimvolokno”, Svetlogorsk, Republic of Belarus), 0.36 mm thick and 1250 m ² / g specific surface area. Activated carbon fabric using electrically conductive glue (preferably silver-containing electrically conductive adhesive on an epoxy basis of the EPO-TEK ^® H20E brand) is glued, preferably, to the polished surface of the substrate, made preferably of a semiconductor material, for example, silicon of the KDB-0.005 (111) grade, doped with boron and having a resistivity of 5 × 10 ^-3 ohm · cm, with a compound providing an electrically conductive adhesive means with the electroconductive substrate of warp yarns and weft activated ugler bottom fabric at the points of abutment (adjoining, touching) to the electrically conductive substrate of their portions that are convexly curved towards the electrically conductive substrate, as well as to ensure that in each adhesive connection the warp and weft threads with the electrically conductive substrate have a maximum penetration depth of the electrically conductive adhesive into the structure of said threads from 0, 3 to 0.5 of their transverse size. It should be noted here that the electrically conductive adhesive used in the operation described above must have the following properties: low electrical resistivity, high adhesion to both the substrate material (in this case, silicon) and carbon; heat resistance in the temperature range of operations by atomic layer deposition, as well as chemical resistance to both the precursors used in atomic layer deposition and the reaction products formed during atomic layer deposition, mainly to ozone, ammonia, hydrogen chloride and water . To carry out this operation, various, preferably inexpensive, equipment can be used, including standard equipment, for example, an EVG ^® 510IS vacuum gluing apparatus, and the temperature-time parameters of this operation unambiguously follow from the corresponding to each used and known from prior art electrically conductive adhesive recommendations for its use. So, when using EPO-TEK ^® H20E electrically conductive adhesive, the activated carbon fabric is bonded to the silicon substrate at a temperature of 150 ° C for 60 minutes and with a residual pressure in the bonding chamber of 10 ² Pa. As for the fulfillment of the mentioned restrictions on the maximum depth of penetration of the electrically conductive adhesive into the structure of the warp and weft activated carbon fabrics in each adhesive connection of these threads to the electrically conductive substrate (namely, from 0.3 to 0.5 of the transverse size of the mentioned threads), they are provided , on the one hand, the appropriate choice (depending on the transverse size of the mentioned yarns) the thickness of the layer of conductive adhesive applied to the front surface of the conductive substrate, and on the other On the other hand, by experimental selection of the pressure applied to the activated carbon fabric, depending on the mechanical parameters of the activated carbon fabric used and on the rheological properties of the used electrically conductive adhesive, to provide immersion in the electrically conductive adhesive of the parts of the warp and weft of activated carbon fabric located with at the same pitch (regularly) in the longitudinal direction of each of the aforementioned filaments and convexly curved towards the conductive substrate, until they adjoin (fit, touch) them to the electrically conductive substrate. To ensure uniform distribution of the clamping force over the entire surface area of the activated carbon fabric, at least the front surface of the electrically conductive substrate, in a preferred embodiment of the invention, is polished.

Thus, instead of the operations used in the prototype related to the formation of a nanostructured coating on the front surface of the substrate in the form of an array of carbon fibers (filaments) with nanometer transverse dimensions and requiring the use of special complex and expensive equipment, only one operation is used, namely, the operation gluing the finished activated carbon fabric to the front surface of the electrically conductive substrate, which does not require either the use of complex and expensive equipment, no significant time costs.

Then, an electrically conductive substrate is heated in an inert atmosphere together with a nanostructured coating located on its front surface to a temperature corresponding to the maximum temperature during atomic layer deposition operations, followed by exposure to it at this temperature until a constant mass is achieved.

Further (similarly to that described in the patent by Bargan V.A. et al. RU 2444078, C1, 2012), the method of atomic layer deposition is applied to the developed surface of a nanostructured coating and conformally the first layer of a dielectric material (amorphous alumina) by feed in alternating sequence of precursors: trimethylaluminum and water under a pressure of 7 mbar. Conformal to the first layer of dielectric material, the second layer of dielectric material (titanium dioxide) is deposited by atomic layer deposition by feeding in an alternating sequence of precursors: titanium tetrachloride and water under a pressure of 7 mbar. The third layer of titanium nitride is applied by atomic layer deposition by feeding in an alternating sequence of precursors: titanium tetrachloride and ammonia under a pressure of 7 mbar, while the first layer is applied at a temperature in the reaction chamber of 270 ÷ 330 ° C; the second layer is applied at a temperature in the reaction chamber of 450 ÷ 500 ° C; the third layer is applied at a temperature in the reaction chamber of 460 ÷ 490 ° C.

и $$M_y^{-1}$$

. В одном из воплощений изобретения при нанесении на развитую поверхность патентуемого наноструктурированного покрытия двух слоев из диэлектрических материалов (Al₂O₃/TiO₂), суммарной толщиной - 134 нм, 67 нм, 34 нм, 17 нм и при размерах электропроводящей подложки, соответствующей каждому конденсатору, в направлении как нитей основы, так и нитей утка, равных 5 мм (при этом $$M_o^{-1}=M_y^{-1}=5мм$$

), емкость готовых конденсаторов составила соответственно - 2000 мкФ, 4000 мкФ, 8000 мкФ, 16000 мкФ, а рабочее напряжение - 80 В, 40 В, 20 В, 10 В. Иными словами, конденсаторы, изготовленные с использованием патентуемого изобретения, могут быть использованы в гибридных аккумуляторно-конденсаторных энергоустановках для автомобилей или солнечных батарей.The obtained multilayer nanocomposite for double-walled capacitors using standard equipment is divided into fragments corresponding to individual capacitors, while the dimensions of the electrically conductive substrate corresponding to each capacitor in the direction of the warp and weft are not less, respectively $$M_o^{-\mathrm{one}}$$

and $$M_y^{-\mathrm{one}}$$

. In one of the embodiments of the invention, when two layers of dielectric materials (Al ₂ O ₃ / TiO ₂ ) are applied to the developed surface of a patented nanostructured coating, with a total thickness of 134 nm, 67 nm, 34 nm, 17 nm and with the dimensions of the electrically conductive substrate corresponding to each capacitor, in the direction of both warp and weft threads, equal to 5 mm ( $$M_o^{-\mathrm{one}}=M_y^{-\mathrm{one}}=5mm$$

), the capacitance of the finished capacitors was 2000 μF, 4000 μF, 8000 μF, 16000 μF, respectively, and the operating voltage was 80 V, 40 V, 20 V, 10 V. In other words, capacitors made using the patented invention can be used in hybrid capacitor banks for cars or solar panels.

The industrial applicability of the patented invention is also confirmed by the fame of the materials used in its implementation, as well as the fame and accessibility of the equipment used.

Claims (3)

1. A multilayer nanocomposite for double-walled capacitors, containing a substrate of an electrically conductive material with a nanostructured coating located on its front surface and being the bottom of the capacitor, as well as at least one layer of dielectric material and a layer of electrically conductive material serving as the upper capacitor lining, formed by atomic layer deposition, characterized in that the nanostructured coating is made in the form of a layer of carbon fabric, warp and weft which are formed by activated carbon fibers, twisted in the longitudinal direction relative to the axis of the corresponding thread with the number of twists - M _o per unit length of warp and with the number of twists -M _y per unit length of weft, warp and weft of the said fabric and electrically by means of an electrically conductive adhesive are connected to the electrically conductive substrate at the points of contact with the electrically conductive substrate of their sections that are convexly curved towards the electrically conductive substrate, while in the house of gluing the warp and weft to the electrically conductive substrate by adhesive, the maximum penetration depth of the electrically conductive glue into the structure of the said yarns is from 0.3 to 0.5 of the transverse size of the threads, and at least the surfaces of the warp and weft fibers are sequentially and conformally , one layer of dielectric material and a layer of electrically conductive material serving as a top cover, the dimensions of the electrically conductive substrate corresponding to each capacitor, for example occurrence of warp yarns and weft yarns respectively at least M _o ^-1 and M _y ^-1. 2. The multilayer nanocomposite according to claim 1, characterized in that the substrate is made of a semiconductor material, for example, silicon, with a polished front surface. 3. A method of manufacturing a multilayer nanocomposite for double-walled capacitors, including the formation on the front surface of an electrically conductive substrate of a nanostructured coating, as well as the application of atomic layer deposition onto a developed surface of a nanostructured coating and conformally at least one layer of a dielectric material and a layer of electrically conductive material, characterized in that activated carbon is used as a nanostructured coating y fabric that is glued to the front surface of the electrically conductive substrate using electrically conductive adhesive to provide bonding of the warp and weft activated carbon fabric by means of an electrically conductive adhesive to the electrically conductive substrate at points adjacent to the electrically conductive substrate of their portions that are convexly curved towards the electrically conductive substrate, and also to provide in each adhesive connection of warp and weft threads with an electrically conductive substrate of maximum penetration depth of the electrically conductive adhesive I have in the structure of the said filaments from 0.3 to 0.5 of their transverse size, and before applying the method of atomic layer deposition onto the developed surface of the nanostructured coating and conformally to it, at least one layer of a dielectric material and a layer of electrically conductive material, the substrate together with a nanostructured coating located on its front surface is heated in an inert atmosphere to a temperature corresponding to the maximum temperature during atomic layer deposition operations, its subsequent exposure at this temperature until a constant mass is achieved.